CN112521221A - Selenium-rich suspension liquid compound fertilizer and preparation method thereof - Google Patents
Selenium-rich suspension liquid compound fertilizer and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B7/00—Fertilisers based essentially on alkali or ammonium orthophosphates
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- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
- C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
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- C05G5/27—Dispersions, e.g. suspensions or emulsions
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Abstract
The invention provides a preparation method of a selenium-rich suspension liquid compound fertilizer, belonging to the field of liquid fertilizers, wherein a macroelement fertilizer such as a nitrogen raw material and the like, a selenium-containing fertilizer and a first suspending agent are stirred and dispersed, and then a modified glutathione hydrolysate is added as a second suspending agent for secondary suspension treatment to prepare the selenium-rich suspension liquid compound fertilizer; the modified suspending agent is prepared by taking the partially hydrolyzed glutathione as a raw material, and a cross-linked three-dimensional network structure is formed in the suspending liquid, so that the suspension stability of the liquid compound fertilizer is greatly improved.
Description
Technical Field
The invention relates to the field of liquid compound fertilizers, in particular to a selenium-rich suspension liquid compound fertilizer and a preparation method thereof.
Background
Selenium is one of indispensable trace elements for human life, can enhance the immunologic function of human body, has the functions of cancer prevention and cancer resistance, also has good effects of preventing and treating diabetes and cardiovascular and cerebrovascular diseases, and can cause various eye diseases due to selenium deficiency. Selenium supplement is the best measure for preventing cancers, but the selenium is not easily absorbed by human bodies when being taken directly, and the best selenium supplement measure is taken from food; the purpose of supplementing selenium can be achieved by eating selenium-rich crops; the selenium content in natural soil is limited and not easy to be absorbed directly by crops.
The suspension fertilizer is a high-concentration liquid fertilizer, is a later product of the liquid fertilizer, and forms two main types of the liquid fertilizer together with a clear liquid fertilizer. The appearance is clear and transparent or semitransparent, namely clear liquid fertilizer. The clear liquid fertilizer has many advantages of the liquid fertilizer, but the clear liquid fertilizer also has the defect of low nutrient content. The low nutrient content limits the transport distance of the clear liquid manure. Typically, clear liquid fertilizers are dispensed and applied nearby. In order to solve the problem of low nutrient content of the clear liquid fertilizer, the transport distance of the liquid fertilizer is enlarged, and then the suspension liquid fertilizer is produced. The suspension liquid fertilizer is a highly concentrated liquid fertilizer, compared with a clear liquid fertilizer, the suspension liquid fertilizer has the advantages that the nutrient content is greatly improved, the nutrition is comprehensive and balanced, the total nutrient content can reach 35-45 percent, even higher, and the total nutrient content can be similar to the nutrient content of a common particle compound fertilizer. Therefore, the transportation cost of the liquid fertilizer with the same amount of nutrients is greatly reduced, and long-distance transportation of the liquid fertilizer becomes possible. The development of the liquid fertilizer industry is greatly facilitated by the production of suspended fertilizers.
Because the concentration requirement of the suspended fertilizer is high, the suspended fertilizer is easy to precipitate after being placed for a long time, the stability and the suspension property are poor, and the suspended fertilizer with high salt content is poor in suspension effect and difficult to produce. Therefore, most of the organic suspended liquid compound fertilizers can only be produced with low nutrient concentration, the standard of the suspended liquid compound fertilizers for high-concentration nutrients is difficult to meet, and the existing suspended fertilizers generally have the problems of large using amount of suspending agents, poor suspension stability, low content of suspended fertilizer nutrients and the like, so that the suspended fertilizers have poor market effects and are difficult to popularize and apply.
Disclosure of Invention
Aiming at the problems, the invention provides a selenium-rich suspension liquid compound fertilizer and a preparation method thereof.
The purpose of the invention is realized by adopting the following technical scheme:
a preparation method of a selenium-rich suspension liquid compound fertilizer comprises the following steps:
s1, weighing urea, ammonium nitrate and selenium-containing fertilizer, dissolving and dispersing the urea, ammonium nitrate and selenium-containing fertilizer in water, raising the temperature of the solution to 40-50 ℃, and stirring for 30-60min to obtain a selenium-containing nitrogen solution, wherein the mass mixing ratio of the urea, the ammonium nitrate, the selenium-containing fertilizer and the water is (2.0-3.2): 2.5-4.0):1 (8-10);
s2, weighing a first suspending agent, adding the first suspending agent into water, heating the solution to 40-50 ℃, fully stirring and dissolving to obtain a first suspension, wherein the mass mixing ratio of the first suspending agent to the water is 1 (15-25), and the first suspending agent comprises high-molecular organic saccharides and/or nonionic surfactants;
s3, sequentially adding a selenium-containing nitrogen solution, powdery macro-elements and trace elements into the first suspension, and fully stirring and dissolving to obtain a first suspension compound fertilizer solution, wherein the mass mixing ratio of the first suspension, the selenium-containing nitrogen solution, the powdery macro-elements and the trace elements is (10-12): 20-32): 10-15): 1;
s4, after the temperature of the first suspension compound fertilizer solution is restored to room temperature and stabilized, slowly adding a plant growth regulator and a second suspension agent, and fully stirring for 60-90min at room temperature to obtain the suspension liquid compound fertilizer, wherein the mass mixing ratio of the first suspension compound fertilizer solution to the plant growth regulator to the second suspension agent is 100 (0.05-0.08) to (1-5); the second suspending agent is a modified glutathione hydrolysate.
Preferably, the selenium-containing fertilizer is one or more of selenite, selenate, selenium-containing minerals and processed products thereof.
Preferably, the high molecular organic saccharide is one or more of sodium alginate, syrup, chitosan and xanthan gum.
Preferably, the powdery macroelement is one or more of monopotassium phosphate, ammonium dihydrogen phosphate, potassium nitrate and potassium chloride; the trace elements are one or more of boric acid, sodium tetraborate, zinc sulfate, EDTA-Mg, EDTA-Zn and EDTA-Fe.
Preferably, the plant growth regulator is one or more of sodium naphthalene acetate, naphthylacetic acid, diethyl aminoethyl hexanoate, brassinolide, compound sodium nitrophenolate, compound potassium nitrophenolate, gibberellin, 6-benzylamino adenine and triacontanol.
Preferably, the preparation method of the modified glutathione hydrolysate comprises the following steps:
s1, adding 6mol/L hydrochloric acid or 4mol/L sulfuric acid solution with the volume of 50% of the glutathione aqueous solution into the glutathione aqueous solution with the mass concentration of 12-18%, heating and refluxing for 1-2h to obtain a partially hydrolyzed product, and freeze-drying to obtain a product A;
s2, dissolving the product A in dicarboxamide which is equal in volume to the glutathione aqueous solution, dropwise adding acetic anhydride which is equal in mass to the glutathione under the condition of ice-water bath, continuously stirring for reaction for 12 hours after dropwise adding is finished, crystallizing by using a mixed solvent of ethyl acetate and n-hexane, wherein the volume ratio of the ethyl acetate to the n-hexane in the mixed solvent is 6:1, and crystallizing to obtain a white powdery product B;
s3, adding triethylamine with the liquid-material ratio of 1ml/g and tetrahydrofuran with the liquid-material ratio of 72-75ml/g into the product B under the ice-water bath condition, dropwise adding pivaloyl chloride with the liquid-material ratio of 1ml/g, controlling the dropwise adding time within 5min, keeping the ice-water bath stirring and reacting for 30min to obtain a solution A,
s4, adding glucosamine hydrochloride into an acetic anhydride solution under the condition of ice-water bath, dropwise adding concentrated sulfuric acid while stirring, stirring and reacting for 20 hours after dropwise adding, adding absolute ethyl alcohol under the condition of ice-water bath till no precipitate is separated out, separating the precipitate, washing with ethyl acetate to obtain a product C, and adding triethylamine with the liquid-material ratio of 1ml/g and tetrahydrofuran with the liquid-material ratio of 72-75ml/g into the product C to obtain a solution B; wherein the mass mixing ratio of the glucosamine hydrochloride, the acetic anhydride and the concentrated sulfuric acid is (1.6-1.7): (8.5-8.8): (1.2-1.5);
and S5, mixing the solution A and the solution B in equal volume under the ice-water bath condition, carrying out heat preservation stirring reaction for 40min, heating to 25 ℃, carrying out heat preservation stirring for 6h, evaporating to remove the solvent, washing the product with absolute ethyl alcohol, and carrying out vacuum drying to obtain the modified glutathione hydrolysate.
Preferably, the second suspending agent further comprises a modified yeast cell wall hydrolysate.
Preferably, the method for preparing the modified yeast cell wall hydrolysate comprises the following steps:
s1, diluting the waste saccharomyces cerevisiae mud with water, filtering out impurities through secondary filtration, separating yeast, rinsing the yeast with 10-20% of sodium chloride solution and clear water respectively, mixing the rinsed yeast with water with the mass of 3-8 times of that of the yeast, heating to boiling, preserving heat for 1-2h, cooling to 40-50 ℃, adding cellulase for enzymolysis, adjusting the pH value of the solution to 6.0-7.0, keeping the temperature, stirring for enzymolysis for 4-8h, and performing ultrasonic crushing to obtain a first product;
wherein the mass ratio of the cellulase to the yeast solution is (0.2-0.4): 100, respectively; the enzyme activity of the cellulase is 15000-50000U/g;
s2, cooling the first product to 35-40 ℃, adding neutral protease and ampullaria gigas digestive enzyme for enzymolysis, keeping the temperature, stirring for enzymolysis for 3-6 hours, and performing enzyme deactivation treatment to obtain a second product;
wherein the mass ratio of the neutral protease, the ampullaria gigas digestive enzyme and the yeast solution is (0.3-0.5): (0.1-0.4): 100, respectively; the enzyme activity of the neutral protease and the ampullaria gigas digestive enzyme is 20000-50000U/g;
s3, separating the precipitate in the second product, centrifugally washing, drying and superfine grinding to obtain a first modified yeast cell wall;
s4, ultrasonically dispersing the first modified yeast cell wall in an ethanol water solution or an isopropanol water solution of an aminosilane coupling agent, wherein the mass concentration of the aminosilane coupling agent is 1g/L, the dispersion liquid-to-liquid ratio is 70-100ml/g, stirring and reacting for 2 hours under the water bath heating condition of 40 ℃, and separating to obtain a second modified yeast cell wall;
s5, slowly dripping diisocyanate into a dimethylamide solution of 2-amino-4-hydroxy-6-methylpyrimidine under an inert protective atmosphere, heating the solution to 80-85 ℃ after dripping is finished, stirring and reacting for 12-14h, adding isovolumetric dimethylamide, adding the second modified yeast cell wall according to the feed-liquid ratio of 50-100ml/g, adding dibutyltin laurate with the mass of 0.1-0.2% of the second modified yeast cell wall, stirring and reacting for 2-4h at 50-55 ℃ under a nitrogen protective atmosphere, and filtering out precipitates after reaction is finished to obtain the modified yeast cell wall hydrolysate;
wherein the mixing molar ratio of the diisocyanate to the 2-amino-4-hydroxy-6-methylpyrimidine to the dicarboxamide is 2:1 (5-7).
Preferably, the aminosilane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane and N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane.
The invention has the beneficial effects that:
(1) the selenium-rich suspension liquid compound fertilizer prepared by adding the selenium-containing fertilizer can be applied to various soil agricultural products, the content of the absorbable selenium in the soil is improved, and the selenium content level in a food chain is optimized.
(2) Aiming at the problem that the existing suspension liquid compound fertilizer is difficult to give consideration to high concentration and suspension effect, the suspension agent of the fertilizer is prepared by modifying partially hydrolyzed glutathione serving as a raw material, good suspension property can be kept at high concentration, specifically, micromolecule polypeptide-glutathione with wide sources is taken as a raw material, micromolecules comprising amino acid, dipeptide and tripeptide are obtained after partial hydrolysis, acetic anhydride and glucosamine are respectively taken as micromolecule end group blocking agents, the induced crystallization effect of the ionicity of the amino acid or the micromolecule polypeptide on the high-concentration fertilizer is reduced, the self-assembly activity of the amino acid and the micromolecule polypeptide serving as biological molecules is utilized, when the second suspension agent is added into the fertilizer and dissolved, the amino acid and the micromolecule polypeptide form a one-dimensional nanofiber structure through non-covalent bond self-assembly, and then the two are mutually crosslinked to form a loose three-dimensional network structure in a disordered or ordered and disordered coexisting manner, meanwhile, based on good hydrophilicity of glucose, the suspended component in the fertilizer solution can be separated from the particle part to be fixed to form the sol-like fertilizer solution, so that the dispersibility and the stability are good, and the suspension effect of the fertilizer is greatly improved.
(3) The modification treatment of the suspending agent can improve the suspending effect, but the suspending liquid is an unstable system, the suspending agent can prolong the suspending time, but still can not avoid the precipitation after long-time standing and storage, the yeast cell wall extracted from industrial waste yeast is taken as a raw material, ureidopyrimidinone is grafted by surface modification treatment and taken as a cross-linking agent of a second suspending agent, and then multiple reversible cross-linking noncovalent bond interaction is formed in the second suspending agent, so that the gelation degree is improved, meanwhile, when the fertilizer is sheared by external force, hydrogen bonds of reversible cross-linking are broken, the fertilizer is converted from a gel state to a sol state, the fluidity is improved, the influence of gelation on the easiness in dilution is reduced, and meanwhile, the suspending agent has good solubility; on the other hand, the modified yeast cell wall has good affinity to the combined selenium, and can play a role of a slow release carrier for the selenium after being added into the compound fertilizer, so that the problems of low availability and easy loss when the selenium concentration is too low are solved, the selenium content in soil is maintained in a stable range, and the high-efficiency absorption of crops to the selenium is promoted.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A preparation method of a selenium-rich suspension liquid compound fertilizer comprises the following steps:
s1, weighing urea, ammonium nitrate and selenium-containing fertilizer, dissolving and dispersing the urea, ammonium nitrate and selenium-containing fertilizer in water, raising the temperature of the solution to 40-50 ℃, and stirring for 30-60min to obtain a selenium-containing nitrogen solution, wherein the mass mixing ratio of the urea, the ammonium nitrate, the selenium-containing fertilizer and the water is (2.0-3.2): 2.5-4.0):1 (8-10), and the selenium-containing fertilizer is selenite, selenate or selenium-containing minerals;
s2, weighing a first suspending agent, adding the first suspending agent into water, heating the solution to 40-50 ℃, and fully stirring and dissolving to obtain a first suspension, wherein the mass mixing ratio of the first suspending agent to the water is 1 (15-25), and the first suspending agent is sodium alginate, syrup, chitosan or xanthan gum;
s3, sequentially adding a selenium-containing nitrogen solution, powdery macro-elements and trace elements into the first suspension, and fully stirring and dissolving to obtain a first suspension compound fertilizer solution, wherein the mass mixing ratio of the first suspension, the selenium-containing nitrogen solution, the powdery macro-elements and the trace elements is (10-12): 20-32): 10-15): 1;
the powdery macroelement is monopotassium phosphate, ammonium dihydrogen phosphate, potassium nitrate or potassium chloride; the trace elements are boric acid, sodium tetraborate, zinc sulfate or EDTA-Zn;
s4, after the temperature of the first suspension compound fertilizer solution is restored to room temperature and stabilized, slowly adding a plant growth regulator and a second suspension agent, and fully stirring for 60-90min at room temperature to obtain the suspension liquid compound fertilizer, wherein the mass mixing ratio of the first suspension compound fertilizer solution to the plant growth regulator to the second suspension agent is 100 (0.05-0.08) to (1-5); the second suspending agent is modified glutathione hydrolysate;
the plant growth regulator is sodium naphthalene acetate, naphthylacetic acid, diethyl aminoethyl hexanoate, brassinolide, compound sodium nitrophenolate, compound potassium nitrophenolate, gibberellin or 6-benzylamino adenine;
the preparation method of the modified glutathione hydrolysate comprises the following steps:
s1, adding 6mol/L hydrochloric acid or 4mol/L sulfuric acid solution with the volume of 50% of the glutathione aqueous solution into the glutathione aqueous solution with the mass concentration of 12-18%, heating and refluxing for 1-2h to obtain a partially hydrolyzed product, and freeze-drying to obtain a product A;
s2, dissolving the product A in dicarboxamide which is equal in volume to the glutathione aqueous solution, dropwise adding acetic anhydride which is equal in mass to the glutathione under the condition of ice-water bath, continuously stirring for reaction for 12 hours after dropwise adding is finished, crystallizing by using a mixed solvent of ethyl acetate and n-hexane, wherein the volume ratio of the ethyl acetate to the n-hexane in the mixed solvent is 6:1, and crystallizing to obtain a white powdery product B;
s3, adding triethylamine with the liquid-material ratio of 1ml/g and tetrahydrofuran with the liquid-material ratio of 72-75ml/g into the product B under the ice-water bath condition, dropwise adding pivaloyl chloride with the liquid-material ratio of 1ml/g, controlling the dropwise adding time within 5min, keeping the ice-water bath stirring and reacting for 30min to obtain a solution A,
s4, adding glucosamine hydrochloride into an acetic anhydride solution under the condition of ice-water bath, dropwise adding concentrated sulfuric acid while stirring, stirring and reacting for 20 hours after dropwise adding, adding absolute ethyl alcohol under the condition of ice-water bath till no precipitate is separated out, separating the precipitate, washing with ethyl acetate to obtain a product C, and adding triethylamine with the liquid-material ratio of 1ml/g and tetrahydrofuran with the liquid-material ratio of 72-75ml/g into the product C to obtain a solution B; wherein the mass mixing ratio of the glucosamine hydrochloride, the acetic anhydride and the concentrated sulfuric acid is (1.6-1.7): (8.5-8.8): (1.2-1.5);
and S5, mixing the solution A and the solution B in equal volume under the ice-water bath condition, carrying out heat preservation stirring reaction for 40min, heating to 25 ℃, carrying out heat preservation stirring for 6h, evaporating to remove the solvent, washing the product with absolute ethyl alcohol, and carrying out vacuum drying to obtain the modified glutathione hydrolysate.
Example 2
Same as example 1, but including 20-40% of modified yeast cell wall hydrolysate in the second suspending agent;
the preparation method of the modified yeast cell wall hydrolysate comprises the following steps:
s1, diluting the waste saccharomyces cerevisiae mud with water, filtering out impurities through secondary filtration, separating yeast, rinsing the yeast with 10-20% of sodium chloride solution and clear water respectively, mixing the rinsed yeast with water with the mass of 3-8 times of that of the yeast, heating to boiling, preserving heat for 1-2h, cooling to 40-50 ℃, adding cellulase for enzymolysis, adjusting the pH value of the solution to 6.0-7.0, keeping the temperature, stirring for enzymolysis for 4-8h, and performing ultrasonic crushing to obtain a first product;
wherein the mass ratio of the cellulase to the yeast solution is (0.2-0.4): 100, respectively; the enzyme activity of the cellulase is 15000-50000U/g;
s2, cooling the first product to 35-40 ℃, adding neutral protease and ampullaria gigas digestive enzyme for enzymolysis, keeping the temperature, stirring for enzymolysis for 3-6 hours, and performing enzyme deactivation treatment to obtain a second product;
wherein the mass ratio of the neutral protease, the ampullaria gigas digestive enzyme and the yeast solution is (0.3-0.5): (0.1-0.4): 100, respectively; the enzyme activity of the neutral protease and the ampullaria gigas digestive enzyme is 20000-50000U/g;
s3, separating the precipitate in the second product, centrifugally washing, drying and superfine grinding to obtain a first modified yeast cell wall;
s4, ultrasonically dispersing the first modified yeast cell wall in an ethanol water solution or an isopropanol water solution of an aminosilane coupling agent, wherein the mass concentration of the aminosilane coupling agent is 1g/L, the dispersion liquid-to-liquid ratio is 70-100ml/g, stirring and reacting for 2 hours under the water bath heating condition of 40 ℃, and separating to obtain a second modified yeast cell wall;
s5, slowly dripping diisocyanate into a dimethylamide solution of 2-amino-4-hydroxy-6-methylpyrimidine under an inert protective atmosphere, heating the solution to 80-85 ℃ after dripping is finished, stirring and reacting for 12-14h, adding isovolumetric dimethylamide, adding the second modified yeast cell wall according to the feed-liquid ratio of 50-100ml/g, adding dibutyltin laurate with the mass of 0.1-0.2% of the second modified yeast cell wall, stirring and reacting for 2-4h at 50-55 ℃ under a nitrogen protective atmosphere, and filtering out precipitates after reaction is finished to obtain the modified yeast cell wall hydrolysate;
wherein the mixing molar ratio of the diisocyanate to the 2-amino-4-hydroxy-6-methylpyrimidine to the dicarboxamide is 2:1 (5-7);
the amino silane coupling agent is gamma-aminopropyl triethoxysilane or gamma-aminopropyl trimethoxysilane.
Example 3
The same as example 1, except that the second suspending agent is the same as the first suspending agent.
Comparative example
The same as example 1, but with only the first suspending agent and without the second suspending agent.
Detection experiment
(1) The indexes of the fertilizer measured by adopting the agricultural industry standard (NY1107-2010) of the people's republic of China are shown in Table 1;
TABLE 1 Fertilizer index test results
| Index (I) | Example 1 | Example 2 | Example 3 | Comparative example |
| Total nitrogen (g/L) | 138.1 | 138.3 | 138.7 | 135.3 |
| Total phosphorus (g/L) | 287.9 | 284.6 | 286.4 | 278.1 |
| Total potassium (g/L) | 187.7 | 187.9 | 191.8 | 176.5 |
| Organic matter (g/L) | 48.9 | 49.7 | 50.4 | 51.2 |
| Selenium (g/L) | 2.4 | 2.5 | 2.4 | 2.4 |
| Density (g/cm)3) | 1.48 | 1.50 | 1.46 | 1.42 |
| Stability at 0 deg.C | No crystallization and no precipitation | No crystallization and no precipitation | No crystallization and no precipitation | Crystallization and precipitation |
| Stability at Normal temperature | No crystallization and no precipitation | No crystallization and no precipitation | No crystal and noPrecipitation of | Crystallization and precipitation |
| Stability at 45 ℃ | No crystallization and no precipitation | No crystallization and no precipitation | No crystallization and no precipitation | Crystallization and precipitation |
(2) The fertilizers prepared in examples 1 to 3 and comparative example were tested for standing stability at normal temperature, and the results are shown in table 2:
TABLE 2 results of stability at ambient temperature
| Time of measurement | Example 1 | Example 2 | Example 3 | Comparative example |
| 10d | No crystallization and no precipitation | No crystallization and no precipitation | No crystallization and no precipitation | Precipitated but not crystallized |
| 30d | No crystallization and no precipitation | No crystallization and no precipitation | No crystallization and no precipitation | Crystallization and precipitation |
| 60d | No crystallization and no precipitation | No crystallization and no precipitation | Precipitated but not crystallized | Crystallization and precipitation |
| 90d | No crystallization and no precipitation | No crystallization and no precipitation | Crystallization and precipitation | Crystallization and precipitation |
| 360d | Precipitated but not crystallized | No crystallization and no precipitation | Crystallization and precipitation | Crystallization and precipitation |
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. The preparation method of the selenium-rich suspension liquid compound fertilizer is characterized by comprising the following steps of:
s1, weighing urea, ammonium nitrate and selenium-containing fertilizer, dissolving and dispersing the urea, ammonium nitrate and selenium-containing fertilizer in water to form a solution, heating the solution to 40-50 ℃, and stirring for 30-60min to obtain a selenium-containing nitrogen solution, wherein the mass mixing ratio of the urea, the ammonium nitrate, the selenium-containing fertilizer and the water is (2.0-3.2): 2.5-4.0):1: (8-10);
s2, weighing a first suspending agent, adding the first suspending agent into water, heating the solution to 40-50 ℃, fully stirring and dissolving to obtain a first suspension, wherein the mass mixing ratio of the first suspending agent to the water is 1 (15-25), and the first suspending agent comprises high-molecular organic saccharides and/or nonionic surfactants;
s3, sequentially adding a selenium-containing nitrogen solution, powdery macro-elements and trace elements into the first suspension, and fully stirring and dissolving to obtain a first suspension compound fertilizer solution, wherein the mass mixing ratio of the first suspension, the selenium-containing nitrogen solution, the powdery macro-elements and the trace elements is (10-12): 20-32): 10-15): 1;
s4, after the temperature of the first suspension compound fertilizer solution is restored to room temperature and stabilized, slowly adding a plant growth regulator and a second suspension agent, and fully stirring for 60-90min at room temperature to obtain the suspension liquid compound fertilizer, wherein the mass mixing ratio of the first suspension compound fertilizer solution to the plant growth regulator to the second suspension agent is 100 (0.05-0.08) to (1-5); the second suspending agent is a modified glutathione hydrolysate.
2. The method for preparing the selenium-enriched suspension liquid compound fertilizer as claimed in claim 1, wherein the selenium-containing fertilizer is one or more of selenite, selenate, selenium-containing minerals and processed products of selenium-containing minerals.
3. The preparation method of the selenium-rich suspension liquid compound fertilizer as claimed in claim 1, wherein the high molecular organic saccharide is one or more of sodium alginate, syrup, chitosan and xanthan gum.
4. The method for preparing the selenium-rich suspension liquid compound fertilizer as claimed in claim 1, wherein the powdery macroelements are one or more of potassium dihydrogen phosphate, ammonium dihydrogen phosphate, potassium nitrate and potassium chloride; the trace elements are one or more of boric acid, sodium tetraborate, zinc sulfate, EDTA-Mg, EDTA-Zn and EDTA-Fe.
5. The method for preparing the selenium-rich suspension liquid compound fertilizer as claimed in claim 1, wherein the plant growth regulator is one or more of sodium naphthalene acetate, naphthylacetic acid, diethyl aminoethyl hexanoate, brassinolide, sodium compound nitrophenolate, potassium compound nitrophenolate, gibberellin, 6-benzylamino adenine and triacontanol.
6. The preparation method of the selenium-rich suspension liquid compound fertilizer as claimed in claim 1, wherein the preparation method of the modified glutathione hydrolysate comprises the following steps:
s1, adding acid liquor with the volume of 50% of the glutathione aqueous solution into the glutathione aqueous solution with the mass concentration of 12-18%, heating and refluxing for 1-2h to obtain a partially hydrolyzed product, and freeze-drying to obtain a product A; wherein the acid solution is 6mol/L hydrochloric acid or 4mol/L sulfuric acid solution;
s2, dissolving the product A in diformylamide with the same volume as the glutathione aqueous solution, dropwise adding acetic anhydride under the condition of ice-water bath, wherein the dropwise adding quality of the acetic anhydride is equal to that of the glutathione in the solution, continuously stirring and reacting for 12 hours after the dropwise adding is finished, transferring the mixture into a mixed solvent of ethyl acetate and n-hexane for crystallization, wherein the volume ratio of the ethyl acetate to the n-hexane in the mixed solvent is 6:1, and crystallizing to obtain a white powdery product B;
s3, adding triethylamine with the liquid-material ratio of 1ml/g and tetrahydrofuran with the liquid-material ratio of 72-75ml/g into the product B under the ice-water bath condition, dropwise adding pivaloyl chloride with the liquid-material ratio of 1ml/g, controlling the dropwise adding time within 5min, keeping the ice-water bath condition and stirring for reaction for 30min to obtain a solution A,
s4, adding glucosamine hydrochloride into an acetic anhydride solution under the condition of ice-water bath, dropwise adding concentrated sulfuric acid while stirring, stirring and reacting for 20 hours after dropwise adding, adding absolute ethyl alcohol under the condition of ice-water bath till the precipitate is not separated out, separating the precipitate and washing with ethyl acetate to obtain a product C, and adding triethylamine with the liquid-material ratio of 1ml/g and tetrahydrofuran with the liquid-material ratio of 72-75ml/g into the product C to obtain a solution B; wherein the mass mixing ratio of the glucosamine hydrochloride, the acetic anhydride and the concentrated sulfuric acid is (1.6-1.7): (8.5-8.8): (1.2-1.5);
s5, mixing the solution A and the solution B in equal volume under the ice-water bath condition, carrying out heat preservation stirring reaction for 40min, heating to 25 ℃, carrying out heat preservation stirring for 6h, carrying out rotary evaporation to remove the solvent to obtain a product, washing the product with absolute ethyl alcohol, and carrying out vacuum drying to obtain the modified glutathione hydrolysate.
7. The method of claim 1, wherein the second suspending agent further comprises a modified yeast cell wall hydrolysate.
8. The method for preparing the selenium-enriched suspended liquid compound fertilizer as claimed in claim 7, wherein the method for preparing the modified yeast cell wall hydrolysate comprises the following steps:
s1, diluting the waste saccharomyces cerevisiae mud with water, filtering out impurities through secondary filtration, separating yeast, rinsing the separated yeast with 10-20% of sodium chloride solution and clean water respectively, mixing the rinsed yeast with water with the mass of 3-8 times that of the yeast, heating to boil, preserving heat for 1-2 hours, cooling to 40-50 ℃, adding cellulase for enzymolysis, adjusting the pH value of the solution to 6.0-7.0, keeping the temperature of 40-50 ℃, stirring for enzymolysis for 4-8 hours, and performing ultrasonic crushing to obtain a first product;
wherein the mass ratio of the cellulase to the yeast solution is (0.2-0.4): 100, respectively; the enzyme activity of the cellulase is 15000-50000U/g;
s2, cooling the first product to 35-40 ℃, adding neutral protease and ampullaria gigas digestive enzyme for enzymolysis, keeping the temperature at 35-40 ℃, stirring for enzymolysis for 3-6 hours, and performing enzyme deactivation treatment to obtain a second product;
wherein the mass ratio of the neutral protease, the ampullaria gigas digestive enzyme and the yeast solution is (0.3-0.5): (0.1-0.4): 100, respectively; the enzyme activity of the neutral protease and the ampullaria gigas digestive enzyme is 20000-50000U/g;
s3, separating the precipitate in the second product, centrifugally washing, drying and superfine grinding to obtain a first modified yeast cell wall;
s4, ultrasonically dispersing the first modified yeast cell wall in an ethanol water solution or an isopropanol water solution of an aminosilane coupling agent, wherein the mass concentration of the aminosilane coupling agent is 1g/L, the dispersion liquid-to-liquid ratio is 70-100ml/g, stirring and reacting for 2 hours under the water bath heating condition of 40 ℃, and separating to obtain a second modified yeast cell wall;
s5, slowly dripping diisocyanate into a dimethylamide solution of 2-amino-4-hydroxy-6-methylpyrimidine under an inert protective atmosphere, heating the solution to 80-85 ℃ after dripping is finished, stirring and reacting for 12-14h, adding isovolumetric dimethylamide, adding the second modified yeast cell wall according to the feed-liquid ratio of 50-100ml/g, adding dibutyltin laurate with the mass of 0.1-0.2% of the second modified yeast cell wall, stirring and reacting for 2-4h at 50-55 ℃ under a nitrogen protective atmosphere, and filtering out precipitates after reaction is finished to obtain the modified yeast cell wall hydrolysate;
wherein the mixing molar ratio of the diisocyanate to the 2-amino-4-hydroxy-6-methylpyrimidine to the dicarboxamide is 2:1 (5-7).
9. The method for preparing the selenium-rich suspension liquid compound fertilizer as claimed in claim 8, wherein the aminosilane coupling agent is one or more of gamma-aminopropyltriethoxysilane, gamma-aminopropyltrimethoxysilane, N-beta (aminoethyl) -gamma-aminopropylmethyldimethoxysilane, and N-beta (aminoethyl) -gamma-aminopropylmethyldiethoxysilane.
10. A selenium-rich suspension liquid compound fertilizer, characterized in that the selenium-rich suspension liquid compound fertilizer is prepared according to the preparation method of one of claims 1 to 9.
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| CN111675574A (en) * | 2020-06-28 | 2020-09-18 | 北部湾海洋新材料研究院 | Slow-release selenium-rich ecological fertilizer for golden camellia and preparation method thereof |
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